U.S. patent number 11,072,835 [Application Number 16/318,978] was granted by the patent office on 2021-07-27 for high-strength seamless stainless steel pipe for oil country tubular goods, and method for producing the same.
This patent grant is currently assigned to JFE Steel Corporation. The grantee listed for this patent is JFE Steel Corporation. Invention is credited to Kenichiro Eguchi, Yasuhide Ishiguro.
United States Patent |
11,072,835 |
Eguchi , et al. |
July 27, 2021 |
High-strength seamless stainless steel pipe for oil country tubular
goods, and method for producing the same
Abstract
Provided herein is a high-strength seamless stainless steel
pipe. The high-strength seamless stainless steel pipe contains, in
mass %, C: 0.05% or less, Si: 0.5% or less, Mn: 0.15 to 1.0%, P:
0.030% or less, S: 0.005% or less, Cr: 14.5 to 17.5%, Ni: 3.0 to
6.0%, Mo: 2.7 to 5.0%, Cu: 0.3 to 4.0%, W: 0.1 to 2.5%, V: 0.02 to
0.20%, Al: 0.10% or less, N: 0.15% or less, and the balance being
Fe and unavoidable impurities. C, Si, Mn, Cr, Ni, Mo, Cu, and N
satisfy a specific formula. Cu, Mo, W, Cr, and Ni satisfy another
specific formula. The high-strength seamless stainless steel pipe
has more than 45% martensite phase, 10 to 45% ferrite phase, and
30% or less retained austenite phase. The total amount of
precipitated Cr, precipitated Mo, and precipitated W is 0.75 mass %
or less.
Inventors: |
Eguchi; Kenichiro (Tokyo,
JP), Ishiguro; Yasuhide (Tokyo, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
JFE Steel Corporation |
Tokyo |
N/A |
JP |
|
|
Assignee: |
JFE Steel Corporation (Tokyo,
JP)
|
Family
ID: |
1000005699535 |
Appl.
No.: |
16/318,978 |
Filed: |
June 14, 2017 |
PCT
Filed: |
June 14, 2017 |
PCT No.: |
PCT/JP2017/021955 |
371(c)(1),(2),(4) Date: |
January 18, 2019 |
PCT
Pub. No.: |
WO2018/020886 |
PCT
Pub. Date: |
February 01, 2018 |
Prior Publication Data
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|
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Document
Identifier |
Publication Date |
|
US 20190292618 A1 |
Sep 26, 2019 |
|
Foreign Application Priority Data
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|
|
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Jul 27, 2016 [JP] |
|
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JP2016-146899 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C22C
38/001 (20130101); C22C 38/48 (20130101); C22C
38/005 (20130101); C22C 38/60 (20130101); C22C
38/06 (20130101); C22C 38/04 (20130101); C22C
38/54 (20130101); C21D 8/10 (20130101); C22C
38/52 (20130101); C22C 38/50 (20130101); C22C
38/002 (20130101); C21D 8/105 (20130101); C21D
6/004 (20130101); C22C 38/02 (20130101); C21D
1/18 (20130101); C21D 9/08 (20130101); C22C
38/46 (20130101); C22C 38/00 (20130101); C22C
38/008 (20130101); C22C 38/42 (20130101); C22C
38/44 (20130101); C21D 2211/005 (20130101); C21D
2211/008 (20130101); C21D 2211/001 (20130101); C21D
2211/004 (20130101) |
Current International
Class: |
C21D
1/18 (20060101); C22C 38/00 (20060101); C22C
38/02 (20060101); C22C 38/04 (20060101); C22C
38/06 (20060101); C21D 6/00 (20060101); C22C
38/44 (20060101); C22C 38/46 (20060101); C22C
38/48 (20060101); C22C 38/50 (20060101); C22C
38/52 (20060101); C22C 38/54 (20060101); C22C
38/60 (20060101); C21D 9/08 (20060101); C21D
8/10 (20060101); C22C 38/42 (20060101) |
Field of
Search: |
;148/592 |
References Cited
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|
Primary Examiner: Walck; Brian D
Attorney, Agent or Firm: RatnerPrestia
Claims
The invention claimed is:
1. A high-strength seamless stainless steel pipe for oil country
tubular goods having a yield strength of 862 MPa or more, the
high-strength seamless stainless steel pipe having a composition
that comprises, in mass %, C: 0.05% or less, Si: 0.5% or less, Mn:
0.15 to 1.0%, P: 0.030% or less, S: 0.005% or less, Cr: 14.5 to
17.5%, Ni: 3.0 to 6.0%, Mo: 2.7 to 5.0%, Cu: 0.3 to 4.0%, W: 1.0%
to 2.5%, V: 0.02 to 0.20%, Al: 0.10% or less, N: 0.15% or less, and
the balance being Fe and unavoidable impurities, and in which the
C, Si, Mn, Cr, Ni, Mo, Cu, and N satisfy the formula (1) below, the
Cu, Mo, W, Cr, and Ni satisfy the formula (2) below, and tempering
conditions during production of the high-strength seamless
stainless steel pipe for oil country tubular goods satisfy the
formula (3) below, the high-strength seamless stainless steel pipe
having a structure comprising more than 45% martensite phase by
volume as a primary phase, and 10 to 45% ferrite phase and 30% or
less retained austenite phase by volume as a secondary phase,
wherein the total amount of precipitated Cr, precipitated Mo, and
precipitated W is 0.75 mass % or less,
-5.9.times.(7.82+27C-0.91Si+0.21Mn-0.9Cr+Ni-1.1Mo+0.2Cu+11N).gtore-
q.13.0 (1), where C, Si, Mn, Cr, Ni, Mo, Cu, and N represent the
contents of corresponding elements (mass %), respectively,
Cu+Mo+W+Cr+2Ni.ltoreq.34.5 (2), where Cu, Mo, W, Cr, and Ni
represent the contents of corresponding elements (mass %),
respectively,
t/(3956-2.9Cr-92.1Mo-50W+61.7Ni+99Cu-5.3T).ltoreq.0.034 (3), where
T is a tempering temperature (.degree. C.), t is a duration of
tempering (min), and Cr, Mo, W, Ni, and Cu represent the contents
of corresponding elements (mass %), respectively.
2. The high-strength seamless stainless steel pipe for oil country
tubular goods according to claim 1, wherein the composition further
comprises, in mass %, at least one selected from Nb: 0.02 to 0.50%,
Ti: 0.02 to 0.16%, Zr: 0.02 to 0.50%, and B: 0.0005 to 0.0030%.
3. The high-strength seamless stainless steel pipe for oil country
tubular goods according to claim 1, wherein the composition further
comprises, in mass %, at least one selected from REM: 0.001 to
0.05%, Ca: 0.001 to 0.005%, Sn: 0.05 to 0.20%, and Mg: 0.0002 to
0.01%.
4. The high-strength seamless stainless steel pipe for oil country
tubular goods according to claim 2, wherein the composition further
comprises, in mass %, at least one selected from REM: 0.001 to
0.05%, Ca: 0.001 to 0.005%, Sn: 0.05 to 0.20%, and Mg: 0.0002 to
0.01%.
5. The high-strength seamless stainless steel pipe for oil country
tubular goods according to claim 1, wherein the composition further
comprises, in mass %, at least one selected from Ta: 0.01 to 0.1%,
Co: 0.01 to 1.0%, and Sb:0.01 to 1.0%.
6. The high-strength seamless stainless steel pipe for oil country
tubular goods according to claim 2, wherein the composition further
comprises, in mass %, at least one selected from Ta: 0.01 to 0.1%,
Co: 0.01 to 1.0%, and Sb:0.01 to 1.0%.
7. The high-strength seamless stainless steel pipe for oil country
tubular goods according to claim 3, wherein the composition further
comprises, in mass %, at least one selected from Ta: 0.01 to 0.1%,
Co: 0.01 to 1.0%, and Sb:0.01 to 1.0%.
8. The high-strength seamless stainless steel pipe for oil country
tubular goods according to claim 4, wherein the composition further
comprises, in mass %, at least one selected from Ta: 0.01 to 0.1%,
Co: 0.01 to 1.0%, and Sb:0.01 to 1.0%.
9. A method for producing the high-strength seamless stainless
steel pipe for oil country tubular goods of claim 1, the method
comprising: heating a steel pipe material; making the steel pipe
material into a seamless steel pipe by hot working; and subjecting
the hot worked seamless steel pipe to quenching and tempering in
sequence, wherein tempering conditions of the tempering are
adjusted so as to satisfy the following formula (3),
t/(3956-2.9Cr-92.1Mo-50W+61.7Ni+99Cu-5.3T).ltoreq.0.034 (3), where
T is the tempering temperature (.degree. C.), t is the duration of
tempering (min), and Cr, Mo, W, Ni, and Cu represent the contents
of corresponding elements (mass %), respectively.
10. A method for producing the high-strength seamless stainless
steel pipe for oil country tubular goods of claim 2, the method
comprising: heating a steel pipe material; making the steel pipe
material into a seamless steel pipe by hot working; and subjecting
the hot worked seamless steel pipe to quenching and tempering in
sequence, wherein tempering conditions of the tempering are
adjusted so as to satisfy the following formula (3),
t/(3956-2.9Cr-92.1Mo-50W+61.7Ni+99Cu-5.3T).ltoreq.0.034 (3), where
T is the tempering temperature (.degree. C.), t is the duration of
tempering (min), and Cr, Mo, W, Ni, and Cu represent the contents
of corresponding elements (mass %), respectively.
11. A method for producing the high-strength seamless stainless
steel pipe for oil country tubular goods of claim 3, the method
comprising: heating a steel pipe material; making the steel pipe
material into a seamless steel pipe by hot working; and subjecting
the hot worked seamless steel pipe to quenching and tempering in
sequence, wherein tempering conditions of the tempering are
adjusted so as to satisfy the following formula (3),
t/(3956-2.9Cr-92.1Mo-50W+61.7Ni+99Cu-5.3T).ltoreq.0.034 (3), where
T is the tempering temperature (.degree. C.), t is the duration of
tempering (min), and Cr, Mo, W, Ni, and Cu represent the contents
of corresponding elements (mass %), respectively.
12. A method for producing the high-strength seamless stainless
steel pipe for oil country tubular goods of claim 4, the method
comprising: heating a steel pipe material; making the steel pipe
material into a seamless steel pipe by hot working; and subjecting
the hot worked seamless steel pipe to quenching and tempering in
sequence, wherein tempering conditions of the tempering are
adjusted so as to satisfy the following formula (3),
t/(3956-2.9Cr-92.1Mo-50W+61.7Ni+99Cu-5.3T).ltoreq.0.034 (3), where
T is the tempering temperature (.degree. C.), t is the duration of
tempering (min), and Cr, Mo, W, Ni, and Cu represent the contents
of corresponding elements (mass %), respectively.
13. A method for producing the high-strength seamless stainless
steel pipe for oil country tubular goods of claim 5, the method
comprising: heating a steel pipe material; making the steel pipe
material into a seamless steel pipe by hot working; and subjecting
the hot worked seamless steel pipe to quenching and tempering in
sequence, wherein tempering conditions of the tempering are
adjusted so as to satisfy the following formula (3),
t/(3956-2.9Cr-92.1Mo-50W+61.7Ni+99Cu-5.3T).ltoreq.0.034 (3), where
T is the tempering temperature (.degree. C.), t is the duration of
tempering (min), and Cr, Mo, W, Ni, and Cu represent the contents
of corresponding elements (mass %), respectively.
14. A method for producing the high-strength seamless stainless
steel pipe for oil country tubular goods of claim 6, the method
comprising: heating a steel pipe material; making the steel pipe
material into a seamless steel pipe by hot working; and subjecting
the hot worked seamless steel pipe to quenching and tempering in
sequence, wherein tempering conditions of the tempering are
adjusted so as to satisfy the following formula (3),
t/(3956-2.9Cr-92.1Mo-50W+61.7Ni+99Cu-5.3T).ltoreq.0.034 (3), where
T is the tempering temperature (.degree. C.), t is the duration of
tempering (min), and Cr, Mo, W, Ni, and Cu represent the contents
of corresponding elements (mass %), respectively.
15. A method for producing the high-strength seamless stainless
steel pipe for oil country tubular goods of claim 7, the method
comprising: heating a steel pipe material; making the steel pipe
material into a seamless steel pipe by hot working; and subjecting
the hot worked seamless steel pipe to quenching and tempering in
sequence, wherein tempering conditions of the tempering are
adjusted so as to satisfy the following formula (3),
t/(3956-2.9Cr-92.1Mo-50W+61.7Ni+99Cu-5.3T).ltoreq.0.034 (3), where
T is the tempering temperature (.degree. C.), t is the duration of
tempering (min), and Cr, Mo, W, Ni, and Cu represent the contents
of corresponding elements (mass %), respectively.
16. A method for producing the high-strength seamless stainless
steel pipe for oil country tubular goods of claim 8, the method
comprising: heating a steel pipe material; making the steel pipe
material into a seamless steel pipe by hot working; and subjecting
the hot worked seamless steel pipe to quenching and tempering in
sequence, wherein tempering conditions of the tempering are
adjusted so as to satisfy the following formula (3),
t/(3956-2.9Cr-92.1Mo-50W+61.7Ni+99Cu-5.3T).ltoreq.0.034 (3), where
T is the tempering temperature (.degree. C.), t is the duration of
tempering (min), and Cr, Mo, W, Ni, and Cu represent the contents
of corresponding elements (mass %), respectively.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
This is the U.S. National Phase application of PCT/JP2017/021955,
filed. Jun. 14, 2017, which claims priority to Japanese Patent
Application No. 2016-146899, filed Jul. 27, 2016, the disclosures
of each of these applications being incorporated herein by
reference in their entireties for all purposes.
FIELD OF THE INVENTION
The present invention relates to a high-strength seamless stainless
steel pipe suitable for use in such as crude oil wells and natural
gas wells (hereinafter, simply referred to as "oil wells").
Particularly, the invention relates to a high-strength seamless
stainless steel pipe suitable for use in oil country tubular goods
and having excellent carbon dioxide corrosion resistance in a very
severe high-temperature corrosive environment containing carbon
dioxide gas (CO.sub.2) and chlorine ions (Cl.sup.-), and excellent
sulfide stress corrosion cracking resistance (SCC resistance) under
high temperature, and excellent sulfide stress cracking resistance
(SSC resistance) at ambient temperature in an environment
containing hydrogen sulfide (H.sub.2S). As used herein,
"high-strength" means strength with a yield strength in the order
of 125 ksi, that is, a yield strength of 862 MPa or more.
BACKGROUND OF THE INVENTION
Recently, rising crude oil prices, and concerned near future
depletion of petroleum resources have prompted active development
of deep oil fields that was unthinkable in the past, and oil fields
and gas fields of a severe corrosive environment, or a sour
environment as it is also called, where hydrogen sulfide and the
like are present. Such oil fields and gas fields are typically very
deep, and involve a severe, high-temperature corrosive environment
of an atmosphere containing CO.sub.2, Cl.sup.-, and H.sub.2S. Steel
pipes for oil country tubular goods intended for use in such an
environment require high strength, and high corrosion resistance
performance (carbon dioxide corrosion resistance, sulfide stress
corrosion cracking resistance, and sulfide stress cracking
resistance).
13Cr martensitic stainless steel pipes are often used for oil
country tubular goods (OCTG) which are used for mining of oil
fields and gas fields of an environment containing carbon dioxide
gas (CO.sub.2), chlorine ions (Cl.sup.-), and the like. Further, in
recent years, modified 13Cr martensitic stainless steels with a
reduced carbon content and increased contents of other components
such as Ni and Mo based on the 13 Cr martensitic stainless steel
are also in wide use.
For example, PTL 1 describes a modified martensitic stainless steel
(pipe) that improves the corrosion resistance of a 13Cr martensitic
stainless steel (pipe). The stainless steel (pipe) described in PTL
1 is a martensitic stainless steel having excellent corrosion
resistance and excellent sulfide stress corrosion cracking
resistance, and contains, in weight %, C: 0.005 to 0.05%, Si: 0.05
to 0.5%, Mn: 0.1 to 1.0%, P: 0.025% or less, S: 0.015% or less, Cr:
10 to 15%, Ni: 4.0 to 9.0%, Cu: 0.5 to 3%, Mo: 1.0 to 3%, Al: 0.005
to 0.2%, N: 0.005% to 0.1%, and the balance being Fe and
unavoidable impurities, in which the Ni equivalent (Ni eq)
satisfies 40C+34N+Ni+0.3Cu-1.1Cr-1.8Mo-10. The martensitic
stainless steel has a tempered martensite phase, a martensite
phase, and a retained austenite phase, wherein the total fraction
of the tempered martensite phase and the martensite phase is 60% or
more and 90% or less, and the remainder is the retained austenite
phase. This improves the corrosion resistance and the sulfide
stress corrosion cracking resistance in a wet carbon dioxide gas
environment, and in a wet hydrogen sulfide environment.
There has been recent development of oil wells in a corrosive
environment of even higher temperatures (as high as 200.degree.
C.). However, with the technique described in PTL 1, the desired
corrosion resistance cannot be sufficiently ensured in a stable
fashion in such a high-temperature corrosive environment.
This has created a demand for a steel pipe for oil country tubular
goods having excellent corrosion resistance and excellent sulfide
stress corrosion cracking resistance even when used in such a
high-temperature corrosive environment and a wide variety of
martensitic stainless steel pipes are proposed.
For example, PTL 2 describes a high-strength stainless steel pipe
with excellent corrosion resistance having a composition
containing, in massa, C: 0.005 to 0.05%, Si: 0.05 to 0.5%, Mn: 0.2
to 1.8%, P: 0.03% or less, S: 0.005% or less, Cr: 15.5 to 18%, Ni:
1.5 to 5%, Mo: 1 to 3.5%, V: 0.02 to 0.2%, N: 0.01 to 0.15%, and O:
0.006% or less, wherein the Cr, Ni, Mo, Cu, and C satisfy a
specific relational expression, and the Cr, Mo, Si, C, Mn, Ni, Cu,
and N satisfy a specific relational expression. The stainless steel
pipe has a structure with a martensite phase as a base phase, and
contains 10 to 60% ferrite phase, and 30% or less austenite phase
by volume in the structure. In this way, the stainless steel pipe
can have sufficient corrosion resistance even in a severe,
CO.sub.2- and Cl.sup.--containing corrosive environment of a
temperature as high as 230.degree. C., and a high-strength and
high-toughness stainless steel pipe for oil country tubular goods
can be stably produced.
PTL 3 describes a high-strength stainless steel pipe for oil
country tubular goods having high toughness and excellent corrosion
resistance. The technique described in PTL 3 produces a steel pipe
of a composition containing, in mass %, C: 0.04% or less, Si: 0.50%
or less, Mn: 0.20 to 1.80%, P: 0.03% or less, S: 0.005% or less,
Cr: 15.5 to 17.5%, Ni: 2.5 to 5.5%, V: 0.20% or less, Mo: 1.5 to
3.5%, W: 0.50 to 3.0%, Al: 0.05% or less, N: 0.15% or less, and O:
0.006% or less, wherein the Cr, Mo, W, and C satisfy a specific
relational expression, the Cr, Mo, W, Si, C, Mn, Cu, Ni, and N
satisfy a specific relational expression, and the Mo and W satisfy
a specific relational expression. Further, the high-strength
stainless steel pipe has a structure with a martensite phase as a
base phase, and contains 10 to 50% ferrite phase by volume in the
structure. The technique enables producing a high-strength
stainless steel pipe for oil country tubular goods having
sufficient corrosion resistance even in a severe, CO.sub.2-,
Cl.sup.--, and H.sub.2S-containing high-temperature corrosive
environment.
PTL 4 describes a high-strength stainless steel pipe having
excellent sulfide stress cracking resistance, and excellent
high-temperature carbon dioxide gas corrosion resistance. The
technique described in PTL 4 produces a steel pipe of a composition
containing, in mass %, C: 0.05% or less, Si: 1.0% or less, P: 0.05%
or less, S: less than 0.002%, Cr: more than 16% and 18% or less,
Mo: more than 2% and 3% or less, Cu: 1 to 3.5%, Ni: 3% or more and
less than 5%, Al: 0.001 to 0.1%, and O: 0.01% or less, wherein the
Mn and N satisfy specific relationship in a range of 1% or less of
Mn, and 0.05% or less of N. The high-strength stainless steel pipe
has a structure that is primarily a martensite phase, and that
contains 10 to 40% ferrite phase, and 10% or less retained .gamma.
phase by volume. The technique enables producing a high-strength
stainless steel pipe having excellent corrosion resistance, which
has the sufficient corrosion resistance even in a carbon dioxide
gas environment of a temperature as high as 200.degree. C., and has
sufficient sulfide stress cracking resistance even at lowered
ambient gas temperatures.
PTL 5 describes a stainless steel for oil country tubular goods
having a proof strength of 758 MPa or more. The stainless steel has
a composition containing, in mass %, C: 0.05% or less, Si: 0.5% or
less, Mn: 0.01 to 0.5%, P: 0.04% or less, S: 0.01% or less, Cr:
more than 16.0 to 18.0%, Ni: more than 4.0 to 5.6%, Mo: 1.6 to
4.0%, Cu: 1.5 to 3.0%, Al: 0.001 to 0.10%, and N: 0.050% or less,
wherein the Cr, Cu, Ni, and Mo satisfy a specific relationship, and
(C+N), Mn, Ni, Cu, and (Cr+Mo) satisfy a specific relationship. The
stainless steel has a structure with a martensite phase and 10 to
40% by volume of ferrite phase, wherein the proportion of the
ferrite phase that crosses a plurality of imaginary segments
measuring 50 .mu.m in length and arranged in a line over a region
of 200 .mu.m from the surface in the thickness direction in a pitch
of 10 .mu.m is larger than 85%. In this way, the stainless steel
for oil country tubular goods has excellent corrosion resistance in
a high-temperature environment, and excellent SSC resistance at
ambient temperature.
PTL 6 describes containing, in mass %, C: 0.05% or less, Si: 0.5%
or less, Mn: 0.15 to 1.0%, P: 0.030% or less, S: 0.005% or less,
Cr: 15.5 to 17.5%, Ni: 3.0 to 6.0%, Mo: 1.5 to 5.0%, Cu: 4.0% or
less, W: 0.1 to 2.5%, and N: 0.15% or less, so as to satisfy
-5.9.times.(7.82+27C-0.91Si+0.21Mn-0.9Cr+Ni-1.1Mo+0.2Cu+11N).gtoreq.13.0,
Cu+Mo+0.5W 5.8, and Cu+Mo+W+Cr+2Ni S 34.5. In this way, the
high-strength seamless stainless steel pipe having excellent
corrosion resistance, which has excellent carbon dioxide corrosion
resistance in a CO.sub.2- and Cl.sup.--containing high-temperature
environment as high as 200.degree. C., and further has excellent
sulfide stress cracking resistance and excellent sulfide stress
corrosion cracking resistance in a H.sub.2S-containing corrosive
environment, can be produced.
PATENT LITERATURE
PTL 1: JP-A-10-1755
PTL 2: JP-A-2005-336595
PTL 3: JP-A-2008-81793
PTL 4: WO2010/050519
PTL 5: WO2010/134498
PTL 6: JP-A-2015-110822
SUMMARY OF THE INVENTION
As the oil fields and gas fields of a severe corrosive environment
are developed, steel pipes for oil country tubular goods are
required to have high strength, and excellent corrosion resistance,
including carbon dioxide corrosion resistance, and sulfide stress
corrosion cracking resistance (SCC resistance) and sulfide stress
cracking resistance (SSC resistance), even in a severe, CO.sub.2,
Cl.sup.--, and H.sub.2S-containing corrosive environment of high
temperatures of 200.degree. C. or more.
However, it is a problem that in the techniques described in PTL 2
to PTL 5, they fail to provide sufficient SSC resistance in an
environment with a high H.sub.2S partial pressure.
It is also a problem that in PTL 2, 3, and 6, they fail to provide
high strength with a yield strength of 862 MPa or more, and high
toughness with an absorption energy at -40.degree. C. of 100 J or
more.
It was found that high toughness with an absorption energy at
-40.degree. C. of 100 J or more cannot be satisfied with the level
of absorption energy, 149 to 197 J at -10.degree. C., described in
the Examples of the specification in PTL 6.
The techniques described in PTL 1 to 6 add large amounts of Cr, Mo,
W, and the like to achieve high corrosion resistance. However,
these elements precipitate as intermetallic compounds during
tempering, and high low-temperature toughness cannot be obtained.
It is a problem that with low low-temperature toughness, the
stainless steel pipes cannot be used in cold climates.
Aspects of the present invention are intended to provide solutions
to the foregoing problems of the related art, and it is an object
according to aspects of the present invention to provide a
high-strength seamless stainless steel pipe for oil country tubular
goods exhibiting high strength and excellent low-temperature
toughness, and having excellent corrosion resistance including
excellent carbon dioxide corrosion resistance, and excellent
sulfide stress corrosion cracking resistance and excellent sulfide
stress cracking resistance, even in a severe corrosive environment
such as described above. Aspects of the invention are also intended
to provide a method for producing such a high-strength seamless
stainless steel pipe.
As used herein, "high-strength" means a yield strength of 125 ksi
(862 MPa) or more.
As used herein, "excellent low-temperature toughness" means having
an absorption energy of 100 J or more at -40.degree. C. as measured
in a Charpy impact test performed with a V-notch test piece (10 mm
thick) according to JIS Z 2242.
As used herein, "excellent carbon dioxide corrosion resistance"
means that a test piece dipped in a test solution: 20 mass % NaCl
aqueous solution (liquid temperature: 200.degree. C.; 30 atm
CO.sub.2 gas atmosphere) charged into an autoclave has a corrosion
rate of 0.125 mm/y or less after 336 hours in the solution.
As used herein, "excellent sulfide stress corrosion cracking
resistance" means that a test piece dipped in a test solution: an
aqueous solution having an adjusted pH of 3.3 with addition of an
aqueous solution of acetic acid and sodium acetate to a 20 mass %
NaCl aqueous solution (liquid temperature: 100.degree. C.; a 30 atm
CO.sub.2 gas and 0.1 atm H.sub.2S atmosphere) and hold in an
autoclave does not crack even after 720 hours under an applied
stress equal to 100% of the yield stress.
As used herein, "excellent sulfide stress cracking resistance"
means that a test piece dipped in a test solution: an aqueous
solution having an adjusted pH of 3.5 with addition of an aqueous
solution of acetic acid and sodium acetate to a 20 mass % NaCl
aqueous solution (liquid temperature: 25.degree. C.; a 0.9 atm
CO.sub.2 gas and 0.1 atm H.sub.2S atmosphere) and hold in an
autoclave does not crack, even after 720 hours under an applied
stress equal to 90% of the yield stress.
In order to achieve the foregoing objects, the present inventors
conducted intensive studies of stainless steel pipes of a
Cr-containing composition from the perspective of corrosion
resistance, with regard to various factors that might affect
low-temperature toughness at -40.degree. C. The studies found that
a high-strength seamless stainless steel pipe having both excellent
carbon dioxide corrosion resistance and excellent high-temperature
sulfide stress corrosion cracking resistance in a high-temperature
corrosive environment as high as 200.degree. C. and containing
CO.sub.2-, Cl.sup.--, and H.sub.2S, and in an environment of a
CO.sub.2, Cl.sup.-, and H.sub.2S-containing corrosive atmosphere
under an applied stress close to the yield strength can be
obtained, when the stainless steel pipe has a structure having a
complex structure that is more than 45% primary martensite phase,
10 to 45% secondary ferrite phase, and 30% or less retained
austenite phase by volume. It was also found that a high-strength
seamless stainless steel pipe having excellent sulfide stress
cracking resistance in a high-concentration H.sub.2S environment
can be obtained, when the stainless steel pipe has the structure
further containing Cr, Mo, and W higher than certain quantities,
respectively.
After further studies, the present inventors found that adjusting
the C, Si, Mn, Cr, Ni, Mo, Cu, and N contents to satisfy the
following formula (1) is important to provide the desired composite
structure in a composition containing 14.5 mass % or more of Cr.
-5.9.times.(7.82+27C-0.91Si+0.21Mn-0.9Cr+Ni-1.1Mo+0.2Cu+11N).gtoreq.13.0,
Formula (1) where C, Si, Mn, Cr, Ni, Mo, Cu, and N represent the
contents of corresponding elements (mass %), respectively.
The left-hand side of the formula (1) is experimentally determined
by the present inventors as an index that indicates the likelihood
of occurrence of the ferrite phase. The present inventors found
that adjusting the alloy elements and the amounts thereof so as to
satisfy the formula (1) is important to achieve the desired complex
structure.
It was also found that excessive generation of retained austenite
can be suppressed, and the desired high-strength and sulfide stress
cracking resistance can be provided by adjusting the Cu, Mo, W, Cr,
and Ni contents to satisfy the following formula (2).
Cu+Mo+W+Cr+2Ni.ltoreq.34.5, Formula (2) where Cu, Mo, W, Cr, and Ni
represent the contents of corresponding elements (massa),
respectively.
As noted above, it was a problem that high low-temperature
toughness may not be obtained when elements such as Cr, Mo, and W
are contained in large quantities because these elements
precipitate as intermetallic compounds during tempering. Addressing
this problem, the present inventors found that excellent
low-temperature toughness with a Charpy absorption energy at
-40.degree. C. of 100 J can be achieved when the total quantity of
the precipitated Cr, precipitated Mo, and precipitated W is 0.75
mass % or less after tempering.
Here, a composition with a high Cr content of 14.5 mass % or more,
and a complex structure of primarily a martensite phase with a
secondary ferrite phase and a retained austenite phase, and further
the composition containing Cr, Mo, and W each in an amount not less
than a specific amount can contribute to not only excellent carbon
dioxide corrosion resistance but excellent sulfide stress corrosion
cracking resistance and excellent sulfide stress cracking
resistance. In this regards, the present inventors think as
follows.
The ferrite phase provides excellent pitting corrosion resistance,
and precipitates in a laminar fashion in the rolling direction,
that is, the axial direction of the pipe. Therefore the laminar
structure is perpendicular to the direction of applied stress in a
sulfide stress crack test, and a sulfide stress corrosion crack
test. Thus, cracks propagate in such a manner that divides the
laminar structure. Accordingly, crack propagation is suppressed,
and the SSC resistance, and the SCC resistance improve.
Excellent carbon dioxide corrosion resistance is achieved when the
composition contains a reduced carbon content of 0.05 mass % or
less, and 14.5 mass % or more of Cr, 3.0 mass % or more of Ni, and
2.7 mass % or more of Mo.
Aspects of the present invention are based on these findings, and
were completed after further studies. Specifically, aspects of the
present invention are as follows.
[1] A high-strength seamless stainless steel pipe for oil country
tubular goods having a yield strength of 862 MPa or more, the
high-strength seamless stainless steel pipe having a composition
that comprises, in mass %, C: 0.05% or less, Si: 0.5% or less, Mn:
0.15 to 1.0%, P: 0.030% or less, S: 0.005% or less, Cr: 14.5 to
17.5%, Ni: 3.0 to 6.0%, Mo: 2.7 to 5.0%, Cu: 0.3 to 4.0%, W: 0.1 to
2.5%, V: 0.02 to 0.20%, Al: 0.10% or less, N: 0.15% or less, and
the balance being Fe and unavoidable impurities, and in which the
C, Si, Mn, Cr, Ni, Mo, Cu, and N satisfy the formula (1) below, and
the Cu, Mo, W, Cr, and Ni satisfy the formula (2) below, the
high-strength seamless stainless steel pipe having a structure
comprising more than 45% martensite phase by volume as a primary
phase, and 10 to 45% ferrite phase and 30% or less retained
austenite phase by volume as a secondary phase, wherein the total
amount of precipitated Cr, precipitated Mo, and precipitated W is
0.75 mass % or less.
-5.9.times.(7.82+27C-0.91Si+0.21Mn-0.9Cr+Ni-1.1Mo+0.2Cu+11N).gtoreq.13.0,
Formula (1) where C, Si, Mn, Cr, Ni, Mo, Cu, and N represent the
contents of corresponding elements (mass %), respectively.
Cu+Mo+W+Cr+2Ni.ltoreq.34.5, Formula (2) where Cu, Mo, W, Cr, and Ni
represent the contents of corresponding elements (mass %),
respectively.
[2] The high-strength seamless stainless steel pipe for oil country
tubular goods according to the item [1], wherein the composition
further comprises, in mass %, at least one selected from Nb: 0.02
to 0.50%, Ti: 0.02 to 0.16%, Zr: 0.02 to 0.50%, and B: 0.0005 to
0.0030%.
[3] The high-strength seamless stainless steel pipe for oil country
tubular goods according to the item [1] or [2], wherein the
composition further comprises, in mass %, at least one selected
from REM: 0.001 to 0.05%, Ca: 0.001 to 0.005%, Sn: 0.05 to 0.20%,
and Mg: 0.0002 to 0.01%.
[4] The high-strength seamless stainless steel pipe for oil country
tubular goods according to any one of the items [1] to [3], wherein
the composition further comprises, in mass %, at least one selected
from Ta: 0.01 to 0.1%, Co: 0.01 to 1.0%, and Sb:0.01 to 1.0%.
[5] A method for producing the high-strength seamless stainless
steel pipe for oil country tubular goods of any one of the items
[1] to [4],
the method comprising:
heating a steel pipe material;
making the steel pipe material into a seamless steel pipe by hot
working; and
subjecting the hot worked seamless steel pipe to quenching and
tempering in sequence,
wherein tempering conditions of the tempering are adjusted so as to
satisfy the following formula (3),
t/(3956-2.9Cr-92.1Mo-50W+61.7Ni+99Cu-5.3T).ltoreq.0.034 (3), where
T is the tempering temperature (.degree. C.), t is the duration of
tempering (min), and Cr, Mo, W, Ni, and Cu represent the contents
of corresponding elements (mass %), respectively.
Aspects of the present invention can provide a high-strength
seamless stainless steel pipe having high strength and excellent
low-temperature toughness, and excellent corrosion resistance
including excellent carbon dioxide corrosion resistance, and
excellent sulfide stress corrosion cracking resistance and
excellent sulfide stress cracking resistance, even in a severe
corrosive environment such as described above.
DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION
A high-strength seamless stainless steel pipe for oil country
tubular goods according to aspects of the present invention has a
composition containing, in massa, C: 0.05% or less, Si: 0.5% or
less, Mn: 0.15 to 1.0%, P: 0.030% or less, S: 0.005% or less, Cr:
14.5 to 17.5%, Ni: 3.0 to 6.0%, Mo: 2.7 to 5.0%, Cu: 0.3 to 4.0%,
W: 0.1 to 2.5%, V: 0.02 to 0.20%, Al: 0.10% or less, N: 0.15% or
less, and the balance being Fe and unavoidable impurities, wherein
the C, Si, Mn, Cr, Ni, Mo, Cu, and N contents are adjusted to
satisfy the following formula (1), and the Cu, Mo, W, Cr, and Ni
contents are adjusted to satisfy the following formula (2).
-5.9.times.(7.82+27C-0.91Si+0.21Mn-0.9Cr+Ni-1.1Mo+0.2Cu+11N).gtoreq.-
13.0, Formula (1) where C, Si, Mn, Cr, Ni, Mo, Cu, and N represent
the contents of corresponding elements (mass %), respectively
Cu+Mo+W+Cr+2Ni.ltoreq.34.5, Formula (2) where Cu, Mo, W, Cr, and Ni
represent the contents of corresponding elements (mass %),
respectively.
The total amount of precipitated Cr, precipitated Mo, and
precipitated W is 0.75 mass % or less after tempering.
The reasons for specifying the composition of the steel pipe
according to aspects of the present invention are as follows. In
the following, "%" means percent by mass, unless otherwise
specifically stated.
C: 0.05% or Less
Carbon is an important element to increase the strength of the
martensitic stainless steel. In accordance with aspects of the
present invention, carbon is desirably contained in an amount of
0.005% or more to provide the desired strength. A carbon content of
more than 0.05% deteriorates the carbon dioxide corrosion
resistance, and the sulfide stress corrosion cracking resistance.
For this reason, the C content is 0.05% or less. The C content is
preferably 0.005 to 0.04%, more preferably 0.005 to 0.02%.
Si: 0.5% or Less
Silicon is an element that acts as a deoxidizing agent. This effect
is obtained with a Si content of 0.1% or more. Si content in excess
of 0.5% deteriorates hot workability. For this reason, the Si
content is 0.5% or less. The Si content is preferably 0.1 to 0.5%,
more preferably 0.2 to 0.3%.
Mn: 0.15 to 1.0%
Manganese is an element that increases steel strength. In
accordance with aspects of the present invention, manganese needs
to be contained in an amount of 0.15% or more to provide the
desired strength. A Mn content in excess of 1.0% deteriorates
toughness. For this reason, the Mn content is 0.15 to 1.0%. The Mn
content is preferably 0.20 to 0.50%, more preferably 0.20 to
0.40%.
P: 0.030% or less
In accordance with aspects of the present invention, phosphorus
should desirably be contained in as small an amount as possible
because this element deteriorates corrosion resistance such as
carbon dioxide corrosion resistance, pitting corrosion resistance,
and sulfide stress cracking resistance. However, a P content of
0.030% or less is acceptable. For this reason, the P content is
0.030% or less, preferably 0.020% or less, more preferably 0.015%
or less. The P content is preferably 0.005% or more because it is
highly costly to make the P content less than 0.005%.
S: 0.005% or Less
Desirably, sulfur should be contained in as small an amount as
possible because this element is highly detrimental to hot
workability, and interferes with a stable operation of the pipe
manufacturing process. However, normal pipe production is possible
when the S content is 0.005% or less. For this reason, the S
content is 0.005% or less, preferably 0.002% or less, more
preferably 0.0015% or less. The S content is preferably 0.0005% or
more because it is highly costly to make the S content less than
0.0005%.
Cr: 14.5 to 17.5%
Chromium is an element that forms a protective coating, and
contributes to improving the corrosion resistance. In accordance
with aspects of the present invention, chromium needs to be
contained in an amount of 14.5% or more to provide the desired
corrosion resistance. With a Cr content of more than 17.5%, the
ferrite fraction becomes overly high, and it is not possible to
provide the desired high strength. It also causes precipitation of
intermetallic compounds during tempering, and deteriorates
low-temperature toughness. For this reason, the Cr content is 14.5
to 17.5%, preferably 15.0 to 17.0%, more preferably 15.0 to
16.5%.
Ni: 3.0 to 6.0%
Nickel is an element that strengthens the protective coating, and
improves the corrosion resistance. Nickel also increases steel
strength through solid solution strengthening. Such effects are
obtained with a Ni content of 3.0% or more. With a Ni content of
more than 6.0%, the stability of the martensite phase decreases,
and the strength decreases. For this reason, the Ni content is 3.0
to 6.0%, preferably 3.5 to 5.5%, more preferably 4.0 to 5.5%.
Mo: 2.7 to 5.0%
Molybdenum is an element that improves resistance to pitting
corrosion due to Cl.sup.- and low pH, and improves the sulfide
stress cracking resistance and the sulfide stress corrosion
cracking resistance. In accordance with aspects of the present
invention, molybdenum needs to be contained in an amount of 2.7% or
more. With a Mo content of less than 2.7%, sufficient corrosion
resistance cannot be obtained in a severe corrosive environment.
Molybdenum is an expensive element, and a large Mo content in
excess of 5.0% causes precipitation of intermetallic compounds, and
deteriorates toughness and corrosion resistance. For this reason,
the Mo content is 2.7 to 5.0%, preferably 3.0 to 5.0%, more
preferably 3.3 to 4.7%. Cu: 0.3 to 4.0%
Copper is an important element that strengthens the protective
coating, and suppresses entry of hydrogen to the steel. Copper also
improves the sulfide stress cracking resistance, and the sulfide
stress corrosion cracking resistance. Copper needs to be contained
in an amount of 0.3% or more to obtain such effects. A Cu content
of more than 4.0% leads to precipitation of CuS at grain
boundaries, and deteriorates hot workability and corrosion
resistance. For this reason, the Cu content is 0.3 to 4.0%,
preferably 1.5 to 3.5%, more preferably 2.0 to 3.0%.
W: 0.1 to 2.5%
Tungsten is a very important element that contributes to improving
steel strength and improves the sulfide stress corrosion cracking
resistance and the sulfide stress cracking resistance. When
contained with molybdenum, tungsten improves the sulfide stress
cracking resistance. Tungsten needs to be contained in an amount of
0.1% or more to obtain such effects. A large W content of more than
2.5% causes precipitation of intermetallic compounds, and
deteriorates toughness. For this reason, the W content is 0.1 to
2.5%, preferably 0.8 to 1.2%, more preferably 1.0 to 1.2%.
V: 0.02 to 0.20%
Vanadium is an element that improves steel strength through
precipitation strengthening. Such an effect can be obtained when
vanadium is contained in an amount of 0.02% or more. A V content of
more than 0.20% deteriorates toughness. For this reason, the V
content is 0.02 to 0.20%, preferably 0.04 to 0.08%, more preferably
0.05 to 0.07%.
Al: 0.10% or Less
Aluminum is an element that acts as a deoxidizing agent. Such an
effect can be obtained when aluminum is contained in an amount of
0.001% or more. With an Al content of more than 0.10%, the oxide
amount becomes excessive, and the toughness deteriorates. For this
reason, the Al content is 0.10% or less, preferably 0.001 to 0.10%,
more preferably 0.01 to 0.06%, even more preferably 0.02 to
0.05%.
N: 0.15% or Less
Nitrogen is an element that highly improves the pitting corrosion
resistance. Such an effect becomes more pronounced when nitrogen is
contained in an amount of 0.01% or more. A nitrogen content of more
than 0.15% results in formation of various nitrides, and the
toughness deteriorates. For this reason, the N content is 0.15% or
less, preferably 0.07% or less, more preferably 0.05% or less.
Preferably, the N content is 0.01% or more.
In accordance with aspects of the present invention, while the
specific components are contained in specific amounts, C, Si, Mn,
Cr, Ni, Mo, Cu, and N satisfy the following formula (1), and Cu,
Mo, W, Cr, and Ni satisfy the following formula (2).
-5.9.times.(7.82+27C-0.91Si+0.21Mn-0.9Cr+Ni-1.1Mo+0.2Cu+11N).gtoreq.13.0
Formula (1)
In the formula (1), C, Si, Mn, Cr, Ni, Mo, Cu, and N represent the
contents of corresponding elements (mass %), respectively.
The left-hand side of the formula (1) represents an index that
indicates the likelihood of occurrence of the ferrite phase. By
containing the alloy elements of formula (1) in adjusted amounts so
as to satisfy the formula (1), a complex structure of the
martensite phase and the ferrite phase or that further including a
retained austenite phase can be stably achieved. The amount of each
alloy element is therefore adjusted to satisfy the formula (1) in
accordance with aspects of the present invention. It should be
noted that when the alloy elements shown in formula (1) are not
contained, the contents of these elements on the left-hand side of
the formula (1) are regarded as 0 percent.
Cu+Mo+W+Cr+2Ni.ltoreq.34.5 Formula (2) In the formula (2), Cu, Mo,
W, Cr, and Ni represent the contents of corresponding elements
(mass %), respectively.
The left-hand side of the formula (2) is newly derived by the
present inventors as an index that indicates the likelihood of
occurrence of the retained austenite. When the value on the
left-hand side of formula (2) exceeds 34.5, an amount of the
retained austenite becomes excessive, and the desired high-strength
cannot be provided. The sulfide stress cracking resistance and the
sulfide stress corrosion cracking resistance also deteriorate. For
this reason, Cu, Mo, W, Cr, and Ni are adjusted to satisfy the
formula (2) in accordance with aspects of the present invention.
The value on the left-hand side of the formula (2) is preferably
32.5 or less, more preferably 31 or less.
The total amount of precipitated Cr, precipitated Mo, and
precipitated W is adjusted to 0.75 mass % or less. The desired
low-temperature toughness cannot be obtained when this value is
more than 0.75%. The total amount of precipitated Cr, precipitated
Mo, and precipitated W is preferably 0.50% or less.
As used herein, "precipitated Cr" refers to chromium carbide,
chromium nitride, chromium carbonitride, or a complex of these,
"precipitated Mo" refers to molybdenum carbide, molybdenum nitride,
molybdenum carbonitride, or a complex of these, and "precipitated
W" refers to tungsten carbide, tungsten nitride, tungsten
carbonitride, or a complex of these.
The amounts of precipitated Cr, precipitated Mo, and precipitated W
can be obtained by measuring the amounts of Cr, Mo, and W in the
residue obtained by using an electroextraction residue method.
The foregoing components are the basic components, and the balance
other than the foregoing components is Fe and unavoidable
impurities. Acceptable as unavoidable impurities is O (oxygen):
0.01% or less.
In addition to the basic components, the following optional
elements may be contained in accordance with aspects of the present
invention, as needed. At least one selected from Nb: 0.02 to 0.50%,
Ti: 0.02 to 0.16%, Zr: 0.02 to 0.50%, and B: 0.0005 to 0.0030%,
and/or at least one selected from REM: 0.001 to 0.05%, Ca: 0.001 to
0.005%, Sn: 0.05 to 0.20%, and Mg: 0.0002 to 0.01%, and/or at least
one selected from Ta: 0.01 to 0.1%, Co: 0.01 to 1.0%, and Sb: 0.01
to 1.0%.
At Least One Selected from Nb: 0.02 to 0.50%, Ti: 0.02 to 0.16%,
Zr: 0.02 to 0.50%, and B: 0.0005 to 0.0030%
Nb, Ti, Zr, and B are elements that contribute to increasing
strength, and, may be contained by being selected, as needed.
In addition to increasing strength as mentioned above, niobium
contributes to improving toughness. Niobium is contained in an
amount of preferably 0.02% or more to provide such effects. A Nb
content of more than 0.50% deteriorates toughness. For this reason,
niobium, when contained, is contained in an amount of 0.02 to
0.50%.
In addition to increasing strength as mentioned above, titanium
contributes to improving sulfide stress cracking resistance.
Titanium is contained in an amount of preferably 0.02% or more to
obtain such effects. When the titanium content is more than 0.16%,
coarse precipitates occur, and the toughness and the sulfide stress
corrosion cracking resistance deteriorate. For this reason,
titanium, when contained, is contained in an amount of 0.02 to
0.16%.
In addition to increasing strength as mentioned above, zirconium
contributes to improving sulfide stress corrosion cracking
resistance. Zirconium is contained in an amount of preferably 0.02%
or more to obtain such effects. A Zr content of more than 0.50%
deteriorates toughness. For this reason, zirconium, when contained,
is contained in an amount of 0.02 to 0.50%.
In addition to increasing strength as mentioned above, boron
contributes to improving hot workability. Boron is contained in an
amount of preferably 0.0005% or more to obtain such effects. A B
content of more than 0.0030% deteriorates toughness, and
deteriorate hot workability. For this reason, boron, when
contained, is contained in an amount of 0.0005 to 0.0030%.
At Least One Selected from REM: 0.001 to 0.05%, Ca: 0.001 to
0.005%, Sn: 0.05 to 0.20%, and Mg: 0.0002 to 0.01%
REM, Ca, Sn, and Mg are elements that contribute to improving
sulfide stress corrosion cracking resistance, and may be contained
by being selected, as needed. The preferred contents for providing
such an effect are 0.001% or more for REM, 0.001% or more for Ca,
0.05% or more for Sn, and 0.0002% or more for Mg. It is not
economically advantageous to contain REM in excess of 0.05%, Ca in
excess of 0.005%, Sn in excess of 0.20%, and Mg in excess of 0.01%
because the effect becomes saturated and is not expected the effect
corresponding to the content. For this reason, REM, Ca, Sn, and Mg,
when contained, are contained in amounts of 0.001 to 0.005%, 0.001
to 0.005%, 0.05 to 0.20%, and 0.0002 to 0.01%, respectively.
At Least One Selected from Ta: 0.01 to 0.1%, Co: 0.01 to 1.0%, and
Sb: 0.01 to 1.0%
Ta, Co, and Sb are elements that contribute to improving carbon
dioxide corrosion resistance (CO.sub.2 corrosion resistance),
sulfide stress cracking resistance, and sulfide stress corrosion
cracking resistance, and may be contained by being selected, as
needed. Cobalt also contributes to raising the Ms point, and
increasing strength. The preferred contents for providing such
effects are 0.01% or more for Ta, 0.01% or more for Co, and 0.01%
or more for Sb. The effect becomes saturated and is not expected
corresponding to the content, when Ta, Co, and Sb are contained in
excess of 0.1%, 1.0%, and 1.0%, respectively. For this reason, Ta,
Co, and Sb, when contained, are contained in amounts of 0.01 to
0.1%, 0.01 to 1.0%, and 0.01 to 1.0%, respectively.
The following describes the reasons for limiting the structure of
the high-strength seamless stainless steel pipe for oil country
tubular goods according to aspects of the present invention.
In addition to the foregoing composition, the high-strength
seamless stainless steel pipe for oil country tubular goods
according to aspects of the present invention has a structure
including more than 45% by volume martensite phase (tempered
martensite phase) as a primary phase (base phase), and 10 to 45% by
volume ferrite phase and 30% or less by volume retained austenite
phase as a secondary phase.
In the seamless steel pipe according to aspects of the present
invention, the base phase is the martensite phase (tempered
martensite phase), and the volume fraction of the martensite phase
is more than 45% to provide the desired high strength. When the
martensite phase is more than 85%, the desired corrosion
resistance, and the desired ductility and toughness may not be
obtained as the contents of the ferrite phase and the retained
austenite phase become smaller. For this reason, the martensite
phase is preferably 85% or less. The martensite phase is primarily
a tempered martensite phase and an as-quenched martensite phase is
preferably 10% or less, if any. In accordance with aspects of the
present invention, in order to provide the desired corrosion
resistance (carbon dioxide corrosion resistance, sulfide stress
cracking resistance (SSC resistance), and sulfide stress corrosion
cracking resistance (SCC resistance)), at least a ferrite phase is
precipitated in the amount of 10 to 45% by volume as a secondary
phase to form a dual phase structure of the martensite phase
(tempered martensite phase) and the ferrite phase. This forms a
laminar structure along the pipe axis direction, and inhibits crack
propagation in thickness direction. The laminar structure does not
form, and the desired improvement of corrosion resistance cannot be
obtained when the ferrite phase is less than 10%. The desired high
strength cannot be provided when the ferrite phase is precipitated
in large quantity of more than 45%. For these reasons, the ferrite
phase as a secondary phase is 10 to 45%, preferably 20 to 40% by
volume.
In addition to the ferrite phase, 30% or less by volume of a
retained austenite phase is precipitated as a secondary phase.
Ductility and toughness improve with the presence of the retained
austenite phase. The desired high strength cannot be provided when
the retained austenite phase is present in abundance with a volume
fraction of more than 30%. Preferably, the retained austenite phase
is 5% or more and 30% or less by volume.
For the measurement of the structure of the seamless steel pipe
according to aspects of the present invention, a test piece for
structure observation is etched with Vilella's reagent (a mixed
reagent containing 2 g of picric acid, 10 ml of hydrochloric acid,
and 100 ml of ethanol), and the structure is imaged with a scanning
electron microscope (magnification: 1,000 times). The structure
fraction of the ferrite phase (volume %) is then calculated with an
image analyzer.
A test piece for X-ray diffraction is prepared by grounding and
polishing so as to provide a measurement cross sectional surface (C
cross section) orthogonal to the pipe axis direction, and the
volume of retained austenite (.gamma.) is measured by X-ray
diffractometry. The retained austenite volume is calculated by
measuring the diffraction X-ray integral intensities of the 7 (220)
plane and the .alpha. (211) plane, and converting the results using
the following equation. .gamma.(volume
fraction)=100/(1+(I.alpha.R.gamma./I.gamma.R.alpha.))
In the equation, I.alpha. represents the integral intensity of
.alpha., R.alpha. represents a crystallographic theoretical value
for .alpha., I.gamma. represents the integral intensity of .gamma.,
and R.gamma. represents a crystallographic theoretical value for
.gamma..
The fraction of the martensite phase is the fraction other than the
ferrite phase and the retained austenite phase.
The structure of the seamless steel pipe according to aspects of
the present invention may be adjusted by a heat treatment
(quenching and tempering) performed under the specific conditions
described below.
A desired method of production of the high-strength seamless
stainless steel pipe for oil country tubular goods according to
aspects of the present invention is described below.
In accordance with aspects of the present invention, a seamless
stainless steel pipe of the composition described above is used as
a starting material. The method of production of the starting
material seamless stainless steel pipe is not particularly limited,
and, typically, any known seamless steel pipe production method may
be used.
Preferably, a molten steel of the foregoing composition is made by
using an ordinary steel making process such as by using a
converter, and formed into a steel pipe material, for example, a
billet, using an ordinary method such as continuous casting, and
ingot casting-blooming. The steel pipe material is heated, and hot
worked using typically a known pipe manufacturing process, for
example, such as the Mannesmann-plug mill process, and the
Mannesmann-mandrel mill process to produce a seamless steel pipe of
the foregoing composition and of the desired dimension's.
After producing the seamless steel pipe, the steel pipe is cooled
to preferably room temperature at a cooling rate faster than air
cooling. This process produces a steel pipe structure having a
martensite phase as a base phase. The seamless steel pipe may be
produced through hot extrusion by pressing.
Here, "cooling rate faster than air cooling" means 0.05.degree.
C./s or more, and "room temperature" means 40.degree. C. or
less.
In accordance with aspects of the present invention, the cooling of
the seamless steel pipe to room temperature at a cooling rate
faster than air cooling is followed by quenching, in which the
steel pipe is heated to a temperature of 850.degree. C. or more,
and cooled to a temperature of 50.degree. C. or less at a cooling
rate faster than air cooling. In this way, the seamless steel pipe
can have a structure containing an appropriate volume of ferrite
phase with a martensite phase as a base phase. Here, "cooling rate
faster than air cooling" means 0.05.degree. C./s or more, and "room
temperature" means 40.degree. C. or less.
The desired high strength cannot be provided when the heating
temperature for quenching is less than 850.degree. C. From the
viewpoint of preventing coarsening of the structure, the heating
temperature for quenching is preferably 1,150.degree. C. or less,
more preferably in the range of 900 to 1,100.degree. C.
The quenching of the seamless steel pipe is followed by tempering,
in which the seamless steel pipe is heated to a tempering
temperature equal to or less than the Ac.sub.1 transformation
point, and cooled (natural cooling). The tempering that heats the
steel pipe to a tempering temperature equal to or less than the
Ac.sub.1 transformation point, and cools the steel pipe produces a
structure having a tempered martensite phase, a ferrite phase, and
a retained austenite phase (retained .gamma. phase). The product is
the high-strength seamless stainless steel pipe having the desired
high strength, high toughness, and excellent corrosion resistance.
When the tempering temperature is high and above the Ac.sub.1
transformation point, the process produces as-quenched martensite,
and fails to provide the desired high strength, high toughness, and
excellent corrosion resistance. Preferably, tempering temperature
is 700.degree. C. or less, preferably 550.degree. C. or more.
The steel containing the predetermined components needs to be
subjected to the tempering process under predetermined conditions
to make the amount of precipitated Cr+precipitated Mo+precipitated
W 0.75% or less. The total amount of precipitated Cr, precipitated
Mo, and precipitated W can become 0.75 mass % or less when the
content of each component is adjusted to satisfy the following
formula (3) that includes the components, tempering temperature,
and tempering time.
t/(3956-2.9Cr-92.1Mo-50W+61.7Ni+99Cu-5.3T).ltoreq.0.034 Formula
(3)
In the formula (3), T represents the tempering temperature
(.degree. C.), and t represents the duration of tempering (min).
Cr, Mo, W, Ni, and Cu represent the contents of corresponding
elements (mass %), respectively.
When the value on the left-hand side of the formula (3) exceeds
0.034, the total amount of precipitated Cr, precipitated Mo, and
precipitated W is larger than 0.75% by mass and the desired
low-temperature toughness cannot be obtained.
EXAMPLES
The present invention is further described below through
Examples.
Molten steels of the compositions shown in Table 1 were produced by
a converter, and cast into billets (steel pipe material) by
continuous casting. The steel pipe material was then hot worked
with a model seamless rolling machine to produce a seamless steel
pipe measuring 83.8 mm in outer diameter and 12.7 mm in wall
thickness. After production, the seamless steel pipe was air
cooled.
A test piece material was cut out from each seamless steel pipe
obtained, and then subjected to quenching in which the test piece
material was heated under the conditions shown in Table 2, and then
cooled. This was followed by tempering, in which the test piece
material was heated under the conditions shown in Table 2, and air
cooled.
A test piece for structure observation was collected from the
quenched and tempered test piece material, and etched with
Vilella's reagent (a mixed reagent containing 2 g of picric acid,
10 ml of hydrochloric acid, and 100 ml of ethanol). The structure
was imaged, with a scanning electron microscope (magnification:
1,000 times), and the structure fraction (volume %) of the ferrite
phase was calculated with an image analyzer.
The structure fraction of the retained austenite phase was measured
using X-ray diffractometry. A measurement test piece was collected
from the quenched and tempered test piece material, and the
diffraction X-ray integrated intensities of the .gamma. (220) plane
and the .alpha. (211) plane were measured by X-ray diffractometry.
The results were then converted using the following equation.
.gamma.(volume
fraction)=100/(1+(I.alpha.R.gamma./I.gamma.R.alpha.))
In the equation, I.alpha. represents the integrated intensity of
.alpha., R.alpha. represents a crystallographic theoretical value
for .alpha., I.gamma. represents the integrated intensity of
.gamma., and R.gamma. represents a crystallographic theoretical
value for .gamma..
The fraction of the martensite phase was calculated as the fraction
other than these phases.
A strip specimen specified by API standard 5CT was collected from
the quenched and tempered test piece material, and subjected to a
tensile test according to the API specifications to determine its
tensile characteristics (yield strength YS, tensile strength TS).
Separately, a V-notch test piece (10 mm thick) was collected from
the quenched and tempered test piece material according to the JIS
Z 2242 specifications. The test piece was subjected to a Charpy
impact test, and the absorption energy at -40.degree. C.,
-20.degree. C. and -10.degree. C. were determined for toughness
evaluation.
The amounts of precipitated Cr, precipitated Mo, and precipitated W
in the state after the heat treatment were investigated using an
electroextraction residue method. In the electroextraction residue
method, a test material was first subjected to galvanostatic
electrolysis in a 10% AA-based electrolytic solution (10 vol %
acetylacetone and 1 mass % tetramethylammonium chloride in
methanol). The resulting electrolytic solution was filtered with a
0.2 .mu.m-mesh filter, and the filtered electrolytic solution was
analyzed using an ICP emission spectral analyzer to measure the
amounts of Cr, Mo, and W in the electrolytic solution. The measured
amounts were used as the amounts of precipitation of these
elements.
A corrosion test piece measuring 3.0 mm in wall thickness, 30 mm in
width, and 40 mm in length was machined from the quenched and
tempered test piece material, and subjected to a corrosion
test.
The corrosion test was conducted by dipping the test piece for 336
hours in a test solution: a 20 mass % NaCl aqueous solution (liquid
temperature: 200.degree. C., a 30 atm CO.sub.2 gas atmosphere)
charged into an autoclave. After the test, the mass of the test
piece was measured, and the corrosion rate was determined from the
calculated weight reduction before and after the corrosion test.
The test piece after the corrosion test was also observed for the
presence or absence of pitting corrosion on a test piece surface
using a loupe (10 times magnification). Corrosion with a pit having
a diameter of 0.2 mm or more was regarded as pitting corrosion.
A round rod-shaped test piece (diameter .PHI.=6.4 mm) was machined
from the quenched and tempered test piece material according to
NACE TM0177, Method A, and subjected to an SSC resistance test.
A 4-point bend test piece measuring 3 mm in wall thickness, 15 mm
in width, and 115 mm in length was collected by machining the
quenched and tempered test piece material, and subjected to an SCC
resistance test.
In the SCC (sulfide stress corrosion crack) resistance test, the
test piece was dipped in a test solution: an aqueous solution
having an adjusted pH of 3.3 with addition of an aqueous solution
of acetic acid and sodium acetate to a 20 mass % NaCl aqueous
solution (liquid temperature: 100.degree. C.; 0.1 atm H.sub.2S and
30 atm CO.sub.2 atmosphere) hold in an autoclave. The test piece
was kept in the solution for 720 hours while applying a stress
equal to 100% of the yield stress. After the test, the test piece
was observed for the presence or absence of cracking.
In the SSC (sulfide stress crack) resistance test, the test piece
was dipped in a test solution: an aqueous solution having an
adjusted pH of 3.5 with addition of an aqueous solution of acetic
acid and sodium acetate to a 20 mass % NaCl aqueous solution
(liquid temperature: 25.degree. C.; 0.1 atm H.sub.2S and 0.9 atm
CO.sub.2 atmosphere). The test piece was kept in the solution for.
720 hours while applying a stress equal to 90% of the yield stress.
After the test, the test piece was observed for the presence or
absence of cracking.
The results are presented in Table 2.
TABLE-US-00001 TABLE 1 Composition (mass %) Value Value on on left-
left- hand hand Nb, REM, side of side of Ti, Ca, Ta, formula
formula Steel Zr, Sn, Co, (1) (2) No. C Si Mn P S Cr Ni Mo Cu V W N
Al B, Mg Sb (*1) (*2) A 0.010 0.21 0.28 0.013 0.0009 15.0 4.7 3.9
2.5 0.048 1.2 0.010 0.016 -- -- - -- 26.7 32.1 B 0.008 0.21 0.28
0.015 0.0008 15.1 4.3 3.5 2.5 0.050 1.2 0.010 0.024 -- -- - -- 27.3
30.8 C 0.014 0.20 0.28 0.014 0.0008 15.4 4.1 3.1 2.5 0.051 1.2
0.015 0.019 -- -- - -- 26.5 30.3 D 0.010 0.20 0.28 0.013 0.0008
16.0 4.5 3.0 2.5 0.051 1.2 0.008 0.024 -- -- - -- 27.2 31.7 E 0.011
0.21 0.28 0.013 0.0010 15.0 3.8 4.5 2.6 0.052 1.2 0.013 0.021 Nb: -
-- -- 35.9 30.9 0.145 F 0.012 0.21 0.28 0.014 0.0012 14.7 4.4 4.3
2.6 0.047 0.9 0.010 0.020 -- -- - -- 28.9 31.3 G 0.011 0.20 0.29
0.015 0.0011 15.8 3.7 3.0 2.8 0.053 0.9 0.007 0.021 -- -- - -- 30.9
29.9 H 0.012 0.20 0.29 0.015 0.0009 15.7 3.8 3.0 2.6 0.056 1.5
0.008 0.025 -- -- - -- 29.4 30.3 I 0.034 0.20 0.29 0.015 0.0010
15.6 3.0 3.0 2.6 0.053 1.2 0.052 0.023 Nb: - -- -- 26.6 28.3 0.056
J 0.007 0.19 0.28 0.016 0.0007 15.1 4.3 3.6 2.6 0.048 1.1 0.008
0.023 -- R- EM: -- 28.0 31.0 0.021, Ca: 0.0021 K 0.009 0.22 0.26
0.015 0.0007 14.9 4.4 3.6 2.5 0.048 1.2 0.010 0.023 -- -- - Ta:
26.2 31.0 0.02, Co: 0.24 L 0.007 0.21 0.26 0.015 0.0009 15.1 4.4
3.4 2.5 0.042 1.1 0.008 0.025 Ti: Sn: -- 26.4 30.9 0.054, 0.13, Zr:
Mg: 0.10 0.0007 M 0.007 0.21 0.26 0.014 0.0008 14.8 4.3 3.6 2.4
0.047 1.1 0.009 0.023 Ti: -- Sb: 26.7 30.5 0.046, 0.14 B: 0.0018 N
0.007 0.20 0.26 0.016 0.0007 14.9 4.3 3.5 2.5 0.046 1.1 0.011 0.022
-- C- a: Ta: 26.3 30.6 0.0020, 0.02, Mg: Sb: 0.0009 0.12 O 0.010
0.21 0.29 0.014 0.0007 15.1 4.5 3.6 2.5 0.042 1.1 0.009 0.023 Zr:
REM: Co: 26.5 31.3 0.08, 0.021, 0.26 B: Sn: 0.0014 0.11 P 0.011
0.23 0.29 0.013 0.0009 15.1 5.5 3.7 2.4 0.051 1.2 0.011 0.014 -- --
- -- 21.2 33.4 Q 0.012 0.20 0.31 0.015 0.0011 15.7 3.7 2.8 3.4
0.043 1.0 0.007 0.021 -- -- - -- 27.8 30.3 R 0.010 0.22 0.28 0.014
0.0009 15.6 3.6 2.9 2.6 0.154 1.6 0.008 0.025 -- -- - -- 30.0 29.9
S 0.038 0.24 0.32 0.015 0.0009 16.8 3.7 2.8 0.9 0.066 1.0 0.044
0.039 Nb: -- -- 30.3 28.9 0.069 T 0.012 0.19 0.30 0.015 0.0010 15.6
3.7 2.9 2.9 0.050 0.8 0.007 0.020 -- -- - -- 28.5 29.6 U 0.012 0.22
0.31 0.013 0.0009 16.1 4.1 4.3 2.6 0.045 1.3 0.015 0.020 -- -- - --
37.9 32.5 V 0.012 0.20 0.29 0.015 0.0008 14.7 2.7 3.0 2.6 0.054 0.9
0.011 0.019 -- -- - -- 30.1 26.7 W 0.033 0.25 0.30 0.015 0.0010
16.4 3.9 2.5 1.0 0.057 1.0 0.045 0.040 -- -- - -- 25.2 28.7 X 0.027
0.24 0.31 0.015 0.0011 17.8 3.7 2.8 1.0 0.052 1.0 0.049 0.044 -- --
- -- 37.0 30.0 Y 0.011 0.23 0.28 0.013 0.0009 14.9 6.2 3.6 2.5
0.050 1.0 0.009 0.015 -- -- - -- 15.3 34.4 Z 0.012 0.21 0.29 0.013
0.0009 14.8 3.7 5.3 2.5 0.044 1.1 0.011 0.019 -- -- - -- 40.2 31.1
AA 0.012 0.20 0.31 0.015 0.0010 15.5 3.5 3.3 4.4 0.059 1.0 0.007
0.019 -- - -- -- 30.1 31.2 AB 0.012 0.21 0.29 0.016 0.0008 14.2 3.1
2.9 2.5 0.060 0.9 0.011 0.020 -- - -- -- 25.0 26.7 AC 0.031 0.23
0.33 0.014 0.0011 16.3 3.7 2.9 0.2 0.059 0.9 0.051 0.037 -- - -- --
29.7 27.7 AD 0.028 0.23 0.32 0.015 0.0009 16.7 4.2 2.9 0.9 0.014
1.0 0.044 0.043 -- - -- -- 29.0 29.9 AE 0.033 0.27 0.32 0.016
0.0010 16.2 3.7 2.8 1.1 0.058 -- 0.039 0.042 -- -- - -- 28.2 27.5
AF 0.009 0.20 0.31 0.019 0.0006 14.6 5.7 2.8 2.1 0.056 0.9 0.008
0.020 -- - -- 12.2 31.8 AG 0.025 0.28 0.33 0.018 0.0006 17.1 5.6
3.3 2.1 0.049 1.4 0.052 0.050 -- - -- -- 24.3 35.1 The balance is
Fe and unavoidable impurities (*1) Value on the left-hand side of
formula (1) = -5.9 .times. (7.82 + 27C - 0.91Si + 0.21Mn - 0.9Cr +
Ni - 1. 1Mo + 0.2Cu +11N) (In the formula, C, Si, Mn, Cr, Ni, Mo,
Cu, and N represent the contents of corresponding elements (mass
%), respectively) (*2) Value on the left-hand side of formula (2) =
Cu + Mo + W + Cr + 2Ni (In the formula, Cu, Mo, W, Cr, and Ni
represent the contents of corresponding elements (mass %),
respectively)
TABLE-US-00002 TABLE 2 Precipitate (mass%) Value on Precipi-
Quenching Tempering left-hand tated Heating Heating side of Cr +
Yield Tensile Steel temper- Dura- temper- Dura- formula Structure
(volume %) Precipi- Precipi- Precipi- Mo + strength strength
Corrosion Steel pipe ature tion ature tion (3) M F A tated tated
tated W YS TS vE.su- b.40 vE.sub.20 vE.sub.10 rate Pitting No. No.
(.degree. C.) (min) (.degree. C.) (min) (*1) (*2) (*2) (*2) Cr Mo W
(*3) (MPa) (MPa) (J) (J) (J) (mm/y)- corrosion SSC SCC Remarks A 1
1050 20 575 30 0.030 61 31 8 0.11 0.21 0.01 0.33 977 1052 154 225
224 - 0.033 Absent .largecircle. .largecircle. Present example B 2
1030 20 575 30 0.030 65 30 5 0.14 0.07 0.01 0.22 952 1012 156 232
261 - 0.035 Absent .largecircle. .largecircle. Present example C 3
1000 20 565 30 0.028 67 29 4 0.06 0.01 0.01 0.08 963 1013 186 228
288 - 0.035 Absent .largecircle. .largecircle. Present example D 4
1000 20 565 30 0.027 61 34 5 0.05 0.01 0.01 0.07 969 1018 130 184
203 - 0.029 Absent .largecircle. .largecircle. Present example E 5
1050 20 570 30 0.033 49 43 8 0.10 0.24 0.01 0.35 954 1066 105 141
209 - 0.033 Absent .largecircle. .largecircle. Present example F 6
1050 20 570 30 0.031 58 35 7 0.09 0.18 0.01 0.28 948 1082 122 182
200 - 0.044 Absent .largecircle. .largecircle. Present example G 7
980 20 590 30 0.031 67 31 2 0.23 0.20 0.07 0.50 886 953 152 214 227
0.- 036 Absent .largecircle. .largecircle. Present example H 8 1000
20 560 30 0.028 66 32 2 0.03 0.01 0.01 0.05 968 1028 156 260 230 -
0.027 Absent .largecircle. .largecircle. Present example I 9 980 20
580 30 0.032 64 30 6 0.18 0.02 0.02 0.22 958 1135 147 224 217 0-
.050 Absent .largecircle. .largecircle. Present example J 10 1030
20 575 30 0.030 66 29 5 0.16 0.10 0.01 0.27 970 1024 126 217 22- 4
0.036 Absent .largecircle. .largecircle. Present example K 11 1030
20 575 30 0.030 65 30 5 0.13 0.09 0.01 0.23 972 1018 160 229 243-
0.032 Absent .largecircle. .largecircle. Present example L 12 1010
20 575 30 0.030 65 32 3 0.15 0.05 0.01 0.21 964 1018 172 247 280-
0.025 Absent .largecircle. .largecircle. Present example M 13 1030
20 575 30 0.031 68 29 3 0.13 0.08 0.01 0.22 926 1021 171 248 276-
0.045 Absent .largecircle. .largecircle. Present example N 14 1030
20 575 30 0.030 64 32 4 0.16 0.07 0.01 0.24 970 1009 153 216 231-
0.033 Absent .largecircle. .largecircle. Present example O 15 1030
20 575 30 0.030 62 32 6 0.13 0.11 0.01 0.25 950 1030 186 255 271-
0.028 Absent .largecircle. .largecircle. Present example P 16 1050
20 575 30 0.029 64 25 11 0.12 0.13 0.01 0.24 916 1062 175 227 27- 7
0.031 Absent .largecircle. .largecircle. Present example Q 17 980
20 590 30 0.029 72 26 2 0.28 0.18 0.08 0.54 931 1053 123 230 208 -
0.031 Absent .largecircle. .largecircle. Present example R 18 1000
20 560 30 0.028 66 31 3 0.03 0.01 0.01 0.05 934 1034 110 205 207-
0.027 Absent .largecircle. .largecircle. Present example S 19 970
20 560 30 0.032 56 38 6 0.03 0.01 0.01 0.05 920 1055 117 151 224 -
0.019 Absent .largecircle. .largecircle. Present example T 20 980
20 590 30 0.030 64 36 0 0.22 0.21 0.06 0.49 958 1007 107 181 203 -
0.034 Absent .largecircle. .largecircle. Present example U 21 1050
20 585 30 0.035 40 46 14 0.24 0.49 0.05 0.78 852 1002 21 105 104-
0.033 Absent .largecircle. .largecircle. Comparative example V 22
960 20 570 30 0.030 69 31 0 0.09 0.01 0.01 0.11 938 1031 77 123 166
0- .068 Absent X X Comparative example W 23 970 20 560 30 0.030 65
30 5 0.02 0.01 0.01 0.04 862 1016 106 154 202 - 0.030 Absent X X
Comparative example X 24 970 20 560 30 0.032 55 36 9 0.02 0.01 0.01
0.04 842 1023 32 114 119 0- .010 Absent .largecircle. .largecircle.
Comparative example Y 25 1050 20 575 30 0.027 67 21 12 0.11 0.10
0.01 0.22 850 1039 230 315 35- 8 0.030 Absent .largecircle.
.largecircle. Comparative example Z 26 1080 20 580 30 0.039 54 36
10 0.17 0.71 0.01 0.89 912 1043 30 117 120- 0.030 Present X X
Comparative example AA 27 980 20 590 30 0.028 59 35 6 0.20 0.27
0.06 0.53 916 1017 131 201 202- 0.038 Absent X X Comparative
example AB 28 960 20 570 30 0.030 65 35 0 0.09 0.01 0.01 0.11 942
1020 115 173 208- 0.139 Present X X Comparative example AC 29 970
20 555 30 0.033 64 33 3 0.01 0.01 0.01 0.03 936 1019 123 215 219-
0.027 Absent X X Comparative example AD 30 970 20 560 30 0.031 62
30 8 0.02 0.01 0.01 0.04 854 1058 122 211 223- 0.016 Absent O O
Comparative example AE 31 970 20 560 30 0.029 67 32 1 0.03 0.01
0.01 0.05 847 1048 157 187 233- 0.024 Present X X Comparative
example AF 32 1000 20 595 30 0.030 80 17 3 0.22 0.27 0.08 0.57 936
1042 241 324 32- 2 0.044 Absent X X Comparative example AG 33 1040
20 550 30 0.026 51 31 18 0.01 0.01 0.01 0.03 852 1034 230 329 3- 01
0.009 Absent .largecircle. .largecircle. Comparative example E 34
1050 20 585 30 0.036 51 40 9 0.24 0.49 0.05 0.78 900 1002 27 106
102 - 0.033 Absent .largecircle. .largecircle. Comparative example
I 35 980 20 600 30 0.035 61 33 6 0.33 0.47 0.13 0.93 879 1081 20
106 103 0- .041 Absent .largecircle. .largecircle. Comparative
example (*1) Value on the left-hand side of formula (3) = t/(3956 -
2.9Cr - 92.1Mo - 50W + 61.7Ni + 99Cu - 5.3T) (T: Tempering
temperature (.degree. C.), t: Duration of tempering (min), Cr, Mo,
W, Ni, and Cu: Content of each element (mass %)) (*2) M: Martensite
phase, F: Ferrite phase, A: Retained austenite phase (*3)
Precipitated Cr + Mo + W: Total amount of precipitated Cr,
precipitated Mo, and precipitated W (mass %)
The high-strength seamless stainless steel pipes of the present
examples all had high strength with a yield strength of 862 MPa or
more, high toughness with an absorption energy at -40.degree. C. of
100 J or more, and excellent corrosion resistance (carbon dioxide
corrosion resistance) in a high-temperature, CO.sub.2- and
Cl.sup.--containing 200.degree. C. corrosive environment. The
high-strength seamless stainless steel pipes of the present
examples produced no cracks (SSC, SCC) in the H.sub.2S-containing
environment, and had excellent sulfide stress cracking resistance,
and excellent sulfide stress corrosion cracking resistance.
On the other hand, comparative examples outside of the range of the
present invention did not have at least one of the desired high
strength, low-temperature toughness, carbon dioxide corrosion
resistance, sulfide stress cracking resistance (SSC resistance),
and sulfide stress corrosion cracking resistance (SCC
resistance).
Steel pipe No. 21 had more than 45% ferrite phase, and the yield
strength YS was less than 862 MPa. The vE-40 value was less than.
0.100 J with the total amount of precipitated Cr, precipitated Mo,
and precipitated W exceeding 0.75% by mass.
Steel pipe No. 22 (steel No. V) had a Ni content of less than 3.0
mass %, and the desired SSC resistance and SCC resistance were not
obtained.
Steel pipe No. 23 (steel No. W) had a Mo content of less than 2.7
mass %, and the desired SSC resistance and SCC resistance were not
obtained.
Steel pipe No. 24 (steel No. X) had a Cr content of more than 17.5
mass %, and the yield strength YS was less than 862 MPa.
Steel pipe No. 25 (steel No. Y) had a Ni content of more than 6.0
mass %, and the yield strength YS was less than 862 MPa.
Steel pipe No. 26 (steel No. Z) had a Mo content of more than 5.0
mass %, and the total amount of precipitated Cr, precipitated Mo,
and precipitated W was more than 0.75% by mass. The vE-40 value was
less than 100 J accordingly. As a result, pitting corrosion
occurred, and the desired SSC resistance and SCC resistance were
not obtained.
Steel pipe No. 27 (steel No. AA) had a Cu content of more than 4.0
mass %, and the desired SSC resistance and SCC resistance were not
obtained.
Steel pipe No. 28 (steel No. AB) had a Cr content of less than 14.5
mass %. As a result, pitting corrosion occurred, and the desired
SSC resistance and SCC resistance were not obtained.
Steel pipe No. 29 (steel No. AC) had a Cu content of less than 0.3
mass %, and the desired SSC resistance and SCC resistance were not
obtained.
Steel pipe No. 30 (steel No. AD) had a V content of less than 0.02
mass %, and the yield strength YS was less than 862 MPa.
Steel pipe No. 31 (steel No. AE) had a W content of less than 0.1
mass %, and the yield strength YS was less than 862 MPa. As a
result, pitting corrosion occurred, and the desired SSC resistance
and SCC resistance were not obtained.
In steel pipe No. 32 (steel No. AF), the value on the left-hand
side of the formula (1) was less than 13.0, and the desired SSC
resistance and SCC resistance were not obtained.
In steel pipe No. 33 (steel No. AG), the value on the left-hand
side of the formula (2) was more than 34.5, and the yield strength
YS was less than 862 MPa.
In steel pipe No. 34, the total amount of precipitated Cr,
precipitated Mo, and precipitated W was more than 0.75% by mass;
and the vE-40 value was less than 100 J.
In steel pipe No. 35, the total amount of precipitated Cr,
precipitated Mo, and precipitated W was more than 0.75% by mass,
and the vE-40 value was less than 100 J.
* * * * *